Polymer-bonded quaterrylene and/or terrylene dyes and compositions containing same

ABSTRACT

Method for increasing at least one of the solubility and dispersibility of a quaterrylene and/or terrylene dye in a liquid medium, including binding the quaterrylene or terrylene dye to a polymer which is soluble in the liquid medium. Various aspects relate without limitation to polymer-bonded quaterrylene or terrylene dyes, processes, markings, security features, articles and dye-doped polymers.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit under 35 U.S.C. §119(e) ofU.S. Provisional Application No. 61/489,891, filed May 25, 2011 andclaims priority under 35 U.S.C. §119 of EP 11167522.9, filed May 25,2011. The entire disclosures of these applications are expresslyincorporated by reference herein.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to polymer-bonded quaterrylene and/orterrylene dyes and compositions such as, e.g., printing inks whichcomprise polymer-bonded quaterrylene and/or terrylene dyes as colorants.

2. Discussion of Background Information

Counterfeiting and market diversion of mass produced goods arefacilitated if the products are handled on a lot base rather than on anindividual item base. In such case counterfeit or diverted products areeasily introduced into the supply chain. Producers and retailers wouldlike to be in a position to distinguish their original products fromsuch counterfeit or diverted (parallel imported or smuggled) products atthe level of the individual unit that is sold.

Further, secure documents such as currency, passports, or identity cardsare increasingly counterfeit around the world. This situation is a verycritical issue for governments and society in general. For examplecriminal organizations may use fake passports or identity cards forhuman beings traffic. As reprographic technologies become more and moresophisticated, it becomes even more difficult to make a cleardistinction between a fake document and the original. Document securityhas therefore a considerable impact on the economy of the countries andalso on the victims of illicit traffic involving counterfeit documents.

In an attempt to prevent counterfeiting marking is currently usedextensively for the recognition, identification and authentication ofindividual items. The marking may be applied, for example, in the formof indicia such as 1-dimensional barcodes, stacked 1-dimensionalbarcodes, 2-dimensional barcodes, 3-dimensional barcodes, a data matrix.and the like. The application of markings is frequently carried out by aprinting process which uses a printing ink with specific opticalproperties that are imparted to the ink by one or more substancescontained therein such as, e.g., luminescent dyes and pigments andcholesteric liquid crystal compounds.

A class of compounds which is suitable for use in, e.g., printing inksfor marking purposes are quaterrylene and terrylene dyes. The parentcompounds quaterrylene and terrylene display fluorescence and there aremany derivatives of quaterrylene and terrylene which are known and maytheoretically be employed as colorants in compositions for marking suchas printing inks and the like. However, a drawback of quaterrylene andterrylene dyes is their often unsatisfactorily low solubility ordispersibility in liquid media such as those which are useful inprinting inks. This low solubility/dispersibility limits the suitabilityof quaterrylene and terrylene dyes as colorants for liquid compositionsin general. It would thus, be advantageous to be able to increase thesolubility and/or dispersibility of quaterrylene and terrylene dyes inliquid media and in particular, liquid media for use in printing inks.

SUMMARY OF THE INVENTION

The present invention provides a method of increasing the solubilityand/or dispersibility of a quaterrylene and/or terrylene dye in a liquidmedium such as, e.g., a liquid medium comprised in a printing inkcomposition. The method comprises binding the quaterrylene and/orterrylene dye to a polymer which is soluble in the liquid medium.

In one aspect of the method, the liquid medium may be a polar liquidmedium.

In another aspect, the quaterrylene and/or terrylene dye may becovalently bonded to the polymer. For example, the polymer may compriseat least one (recurring) monomer unit that comprises at least one polargroup which may, for example, be selected from hydroxy, carboxy andamino groups. Accordingly, the polymer may, for example, comprise aphenolic resin such as, e.g., a phenolic resin of formula

wherein the groups R₄ may be the same or different and are selected fromalkyl groups having from 1 to about 10 carbon atoms and the averagenumber of m is from about 1 to about 30, for example, from about 1 toabout 25, from about 1 to about 15, from about 1 to about 10, from about1 to about 5, from about 1 to about 3, from about 5 to about 15, fromabout 5 to about 10, from about 10 to about 20, or from about 20 toabout 30. The groups R₄ may be the same or different (preferably thesame) and may, for example, be selected from tert-butyl, tert-octyl andbranched nonyl. Further, a group R₄ may be in the meta- or para-positionwith respect to the OH group (in formula (D) only the para position isshown), and there may be more than one group R₄ (e.g., 2 or 3 groups R₄)present on a phenyl ring. For example, if two groups R₄ are present on aphenyl ring (the same or different, preferably the same groups R₄) theymay be present in any of the available positions on the phenyl ring,such as, e.g., meta/para or meta/meta.

In another aspect of the method of the present invention, thequaterrylene and/or terrylene dye may be bonded to the polymer byreacting a group comprised in the quaterrylene and/or terrylene dye withthe at least one (preferably) polar group of the polymer. The at leastone polar group may, for example, be a hydroxy group and/or the groupcomprised in the quaterrylene and/or terrylene dye may be a halogen suchas, e.g., Br or Cl.

In a still further aspect of the method of the present invention, thequaterrylene and/or terrylene dye may be a compound of formula (A),formula (B) or formula (C) below:

wherein:the groups Z, the same or different from each other, represent O, S orN—R, provided that in the above formulae the unit —CO—Z—CO— (in the caseof formula (A) or formula (B) one or both units of formula —CO—Z—CO—)may be replaced by a unit —CS—Z—CO—, or a unit —CS—Z—CS—, or by [—COOHHOOC—] (i.e., the dicarboxylic acid instead of the cyclic anhydride) andfurther provided that for Z═N—R a unit —CO—Z—CO— may be replaced by aunit of formula —C(═NR′)—NR—CO—;R and R′ independently represent an optionally substituted aliphatic,cycloaliphatic, aromatic, heteroaromatic, alkylaryl, alkylheteroaryl,arylalkyl or heteroarylalkyl group having from 1 to about 20 carbonatoms; and R and R′ may also be combined to form, together with the Natoms to which they are attached, an optionally substituted and/or fused5- to 7-membered ring;the groups X may be the same or different and represent halogen, COOH,and isocyanate (NCO);the groups Y may be the same or different and are selected from OH, NO₂,CN, groups of formula R″, OR″, COOR″, OCOR″, CONHR″, CO(NR″)₂, OCONHR″,OCO(NR″)₂, COR″, SO₃H, SO₃R″, SO₂NHR″, SO₂N(R″)₂, NHCOR″, NRCOR″,NHCOOR″, NRCOOR″, NHSO₂R″, NRSO₂R″, NHR″, and N(R″)₂, wherein the groupsR″ may be the same or different and represent an optionally substitutedaliphatic, cycloaliphatic, aromatic, heteroaromatic, alkylaryl,alkylheteroaryl, arylalkyl or heteroarylalkyl group having from 1 toabout 20 carbon atoms and, where two groups R″ are present, may also becombined to form, together with the N atom to which they are attached,an optionally substituted and/or fused 5- to 7-membered ring;n and p each represent 0 or an integer of from 1 to 8 (i.e., 1, 2, 3, 4,5, 6, 7 or 8), provided that (n+p) is not higher than 8 and furtherprovided that for n=0 at least one of R, R′ and R″ comprises at leastone group X as substituent.

In one aspect of the compounds of the above formulae, the (only) group Zor at least one of the groups Z represents N—R wherein R may beselected, for example, from optionally substituted alkyl having from 1to about 6 carbon atoms, optionally substituted alkylaryl or arylalkylhaving from 7 to about 12 carbon atoms, optionally substituted arylhaving from about 6 to about 20 carbon atoms, and optionally substitutedheteroaryl having from about 3 to about 20 carbon atoms such as, e.g.,from optionally substituted alkyl having from 1 to about 4 carbon atoms,optionally substituted phenyl, or optionally substituted benzyl. By wayof non-limiting example, R may represent phenyl substituted with from 1to about 3 groups selected from halogen and alkyl having from 1 to about6 carbon atoms such as, e.g., a phenyl group substituted by at least twoalkyl groups which comprise a secondary or tertiary carbon atom,examples of which include isopropyl and tert.-butyl groups.

In another aspect of the compounds of the above formulae, thequaterrylene and/or terrylene dye may be a compound of formula (C).Alternatively, the quaterrylene and/or terrylene dye may be a compoundof formula (A) or formula (B) such as, e.g., a compound of formula (A)or formula (B) wherein the groups Z may be the same or different andrepresent O or N—R (including compounds wherein both groups Z are O,compounds wherein both groups Z are N—R (with the groups R being thesame or different), and compounds wherein one group Z is O and the othergroup Z is N—R).

The present invention also provides a quaterrylene and/or terrylene dyewhose solubility and/or dispersibility in a polar liquid medium has beenincreased by having been bonded to a polymer, as well as apolymer-bonded quaterrylene and/or terrylene dye of formula (A) orformula (B) or formula (C):

whereinthe groups Z, the same or different from each other, represent O, S orN—R, provided that the unit —CO—Z—CO— (in the case of formula (A) orformula (B) one unit or both units) may be replaced by —CS—Z—CO— or aunit —CS—Z—CS—, or may be replaced by [—COOH HOOC—] (i.e., thedicarboxylic acid instead of the anhydride) and further provided thatfor Z═N—R a unit —CO—Z—CO— may be replaced by a unit of formula—C(═NR′)—NR—CO—;R and R′ independently represent an optionally substituted aliphatic,cycloaliphatic, aromatic, heteroaromatic, alkylaryl, alkylheteroaryl,arylalkyl or heteroarylalkyl group having from 1 to about 20 carbonatoms; and R and R′ may be combined to form, together with the N atomsto which they are attached, an optionally substituted and/or fused 5- to7-membered ring;the groups X may be the same or different and represent halogen,isocyanate and COOH, with the proviso that at least one group X (whichmay be the only group X) represents a group of formula -L-P wherein Lrepresents a covalent (direct) bond or a bridging group and P representsa polymer molecule;the groups Y may be the same or different and are selected from OH, NO₂,CN, groups of formula R″, OR″, COOR″, OCOR″, CONHR″, CO(NR″)₂, OCONHR″,OCO(NR″)₂, COR″, SO₃H, SO₃R″, SO₂NHR″, SO₂N(R″)₂, NHCOR″, NRCOR″,NHCOOR″, NRCOOR″, NHSO₂R″, NRSO₂R″, NHR″, and N(R″)₂, wherein the groupsR″ may be the same or different and represent an optionally substitutedaliphatic, cycloaliphatic, aromatic, heteroaromatic, alkylaryl,alkylheteroaryl, arylalkyl or heteroarylalkyl group having from 1 toabout 20 carbon atoms and, where two groups R″ are present, may also becombined to form, together with the N atom to which they are attached,an optionally substituted and/or fused 5- to 7-membered ring;n and p each represent 0 or an integer of from 1 to 8 (i.e., 1, 2, 3, 4,5, 6, 7 or 8), provided that (n+p) is not higher than 8 and furtherprovided that for n=0 at least one of R, R′ and R″ comprises at leastone group X as substituent.

In one aspect of the polymer-bonded quaterrylene and/or terrylene dye ofthe present invention, the (only) group Z or at least one of the groupsZ (in the case of formula (A) and formula (B)) represents N—R wherein Rmay be selected, for example, from optionally substituted alkyl havingfrom 1 to about 6 carbon atoms, optionally substituted alkylaryl orarylalkyl having from 7 to about 12 carbon atoms, optionally substitutedaryl having from about 6 to about 20 carbon atoms, and optionallysubstituted heteroaryl having from about 3 to about 20 carbon atoms suchas, e.g., from optionally substituted alkyl having from 1 to about 4carbon atoms, optionally substituted phenyl, or optionally substitutedbenzyl. By way of non-limiting example, R may represent phenylsubstituted with from 1 to about 3 groups selected from halogen andalkyl having from 1 to about 6 carbon atoms such as, e.g., a phenylgroup substituted by at least two alkyl groups which comprise asecondary or tertiary carbon atom, non-limiting examples of whichinclude isopropyl and tert.-butyl groups.

In another aspect of the polymer-bonded quaterrylene and/or terrylenedye of the present invention, the quaterrylene and/or terrylene dye maybe a compound of formula (A) or formula (B) or formula (C).Alternatively, the polymer-bonded quaterrylene and/or terrylene dye maybe a compound of formula (A) or formula (B) such as, e.g., a compound offormula (A) or formula (B) wherein the groups Z may be the same ordifferent and represent O or N—R (including compounds wherein bothgroups Z are O, compounds wherein both groups Z are N—R (the groups Rbeing the same or different) and compounds wherein one group Z is O andthe other group Z is N—R).

In yet another aspect of the polymer-bonded quaterrylene and/orterrylene dye of the present invention, L may be selected from O,C(═O)O, OC(═O), C(═O)NH, NHC(═O)O, NHC(═O)NH and C(═)O—O—C(═O). Forexample, L may represent O.

In a still further aspect of the polymer-bonded quaterrylene and/orterrylene dye of the present invention, P may represent a polymermolecule that comprises at least one (recurring) monomer unit thatcomprises at least one polar group such as, e.g., at least one polargroup selected from hydroxy, carboxy and amino groups. By way ofnon-limiting example, the polymer may comprise a phenolic resin such as,e.g., a phenolic resin of formula

wherein the groups R₄ may be the same or different and are selected fromalkyl groups having from 1 to about 10 carbon atoms and the averagenumber of m is from about 1 to about 30, for example, from about 1 toabout 25, from about 1 to about 15, from about 1 to about 10, from about1 to about 5, from about 1 to about 3, from about 5 to about 15, fromabout 5 to about 10, from about 10 to about 20, or from about 20 toabout 30. The groups R₄ may be the same or different (preferably thesame) and may, for example, be selected from tert-butyl, tert-octyl andbranched nonyl. Further, a group R₄ may be in the meta- or para-positionwith respect to the OH group (in formula (D) only the para position isshown), and there may be more than one group R₄ (e.g., 2 or 3 groups R₄)present on a phenyl ring. For example, if two groups R₄ are present on aphenyl ring (the same or different, preferably the same groups R₄) theymay be present in any of the available positions on the phenyl ring,such as, e.g., meta/para or meta/meta.

In another aspect of the polymer-bonded quaterrylene and/or terrylenedye of the present invention, P may have one or more than onequaterrylene and/or terrylene dye molecule bonded thereto.

The present invention also provides a process for making apolymer-bonded quaterrylene and/or terrylene dye as set forth above(including the various aspects thereof). The process comprisescontacting at least one quaterrylene and/or terrylene dye of formulae(A) to (C):

wherein the groups Z, the same or different from each other, representO, S or N—R, provided that the unit —CO—Z—CO—(in the case of formula (A)or formula (B) one or both units) may be replaced by —CS—Z—CO— or a unit—CS—Z—CS—, or may be replaced by [—COOH HOOC—] (i.e., the dicarboxylicacid instead of the anhydride) and that for Z═N—R the unit —CO—Z—CO— maybe replaced by a unit of formula —C(═NR′)—NR—CO—;R and R′ in the above formulae (A) and (B) and (C) independentlyrepresent an optionally substituted aliphatic, cycloaliphatic, aromatic,heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkylgroup having from 1 to about 20 carbon atoms; and R and R′ may also becombined to form, together with the N atoms to which they are attached,an optionally substituted and/or fused 5- to 7-membered ring;the groups X may be the same or different and represent halogen,isocyanate and COOH;the groups Y may be the same or different and are selected from OH, NO₂,CN, groups of formula R″, OR″, COOR″, OCOR″, CONHR″, CO(NR″)₂, OCONHR″,OCO(NR″)₂, COR″, SO₃H, SO₃R″, SO₂NHR″, SO₂N(R″)₂, NHCOR″, NRCOR″,NHCOOR″, NRCOOR″, NHSO₂R″, NRSO₂R″, NHR″, and N(R″)₂, wherein the groupsR″ may be the same or different and represent an optionally substitutedaliphatic, cycloaliphatic, aromatic, heteroaromatic, alkylaryl,alkylheteroaryl, arylalkyl or heteroarylalkyl group having from 1 toabout 20 carbon atoms and may also be combined to form, together withthe N atom to which they are attached, an optionally substituted and/orfused 5- to 7-membered ring;n and p each represent 0 or an integer of from 1 to 8 (i.e., 1, 2, 3, 4,5, 6, 7 or 8), provided that (n+p) is not higher than 8, and furtherprovided that for n=0 at least one of R, R′ and R″ comprises at leastone group X as substituent;with a polymer P under conditions which cause a reaction of a (at leastone) group X of the quaterrylene and/or terrylene dye with a functionalgroup of the polymer to covalently bind the polymer to the quaterryleneand/or terrylene dye.

In one aspect of the process, a group X of the quaterrylene and/orterrylene dye that represents halogen may be caused to react with an OHgroup of the polymer P to replace X by a group —O—P. For example, the OHgroup of the polymer may be a phenolic OH group.

In another aspect of the process of the present invention, the processmay be carried out in the presence of a base.

The present invention also provides a polymer-bonded quaterrylene and/orterrylene dye of one of formulae (I) to (IX):

whereinthe groups Z, the same or different from each other, represent O, S orN—R, provided that in the above formulae the unit —CO—Z—CO—(in the caseof formula (I) or (II) one or both units of formula —CO—Z—CO—) may bereplaced by a unit —CS—Z—CO—, or a unit —CS—Z—CS—, or by [—COOH HOOC—](i.e., the dicarboxylic acid instead of the cyclic anhydride) andfurther provided that for Z═N—R a unit —CO—Z—CO— may be replaced by aunit of formula —C(═NR′)—NR—CO—;R and R′ independently represent an optionally substituted aliphatic,cycloaliphatic, aromatic, heteroaromatic, alkylaryl, alkylheteroaryl,arylalkyl or heteroarylalkyl group having from 1 to about 20 carbonatoms; and R and R′ may be combined to form, together with the N atomsto which they are attached, an optionally substituted and/or fused 5- to7-membered ring;R₁, R₂ and R₃ are independently selected from hydrogen, optionallysubstituted C₁-C₄ alkyl, optionally substituted C₁-C₄ alkyl-COOH,optionally substituted C₁-C₄ alkyl-SO₃H, optionally substituted C₁-C₄alkoxy, optionally substituted mono(C₁-C₄)alkylamino, optionallysubstituted di(C₁-C₄)alkylamino, optionally substituted C₁-C₄aminoalkyl, halogen, cyano, nitro, and SO₃H;the groups X may be the same or different and represent halogen,isocyanate and COOH;the groups Y may be the same or different and are selected from OH, NO₂,CN, groups of formula R″, OR″, COOR″, OCOR″, CONHR″, CO(NR″)₂, OCONHR″,OCO(NR″)₂, COR″, SO₃H, SO₃R″, SO₂NHR″, SO₂N(R″)₂, NHCOR″, NRCOR″,NHCOOR″, NRCOOR″, NHSO₂R″, NRSO₂R″, NHR″, and N(R″)₂, wherein the groupsR″ may be the same or different and represent an optionally substitutedaliphatic, cycloaliphatic, aromatic, heteroaromatic, alkylaryl,alkylheteroaryl, arylalkyl or heteroarylalkyl group having from 1 toabout 20 carbon atoms and, where two groups R″ are present, may also becombined to form, together with the N atom to which they are attached,an optionally substituted and/or fused 5- to 7-membered ring;in the case of formulae (V), (VII) and (IX) n and p each represent 0 oran integer of from 1 to 8 (i.e., 1, 2, 3, 4, 5, 6, 7 or 8), providedthat (n+p) is not higher than 8; and in the case of the remainingformulae n and p each represent 0 or an integer of from 1 to 7 (i.e., 1,2, 3, 4, 5, 6 or 7), provided that (n+p) is not higher than 7.P represents a polymer molecule.

In one aspect of the above polymer-bonded quaterrylene and/or terrylenedye, P may represent a polymer molecule that comprises at least onemonomer unit that comprises at least one polar group such as, e.g., agroup selected from hydroxy, carboxy and amino groups. By way ofnon-limiting example, the polymer may comprise a phenolic resin such as,e.g., a resin of formula

wherein the groups R₄ may be the same or different and are selected fromalkyl groups having from 1 to about 10 carbon atoms and the averagenumber of m is from about 1 to about 30, for example, from about 1 toabout 25, from about 1 to about 15, from about 1 to about 10, from about1 to about 5, from about 1 to about 3, from about 5 to about 15, fromabout 5 to about 10, from about 10 to about 20, or from about 20 toabout 30. The groups R₄ may be the same or different (preferably thesame) and may, for example, be selected from tert-butyl, tert-octyl andbranched nonyl. Further, a group R₄ may be in the meta- or para-positionwith respect to the OH group (in formula (D) only the para position isshown), and there may be more than one group R₄ (e.g., 2 or 3 groups R₄)present on a phenyl ring. For example, if two groups R₄ are present on aphenyl ring (the same or different, preferably the same groups R₄) theymay be present in any of the available positions on the phenyl ring,such as, e.g., meta/para or meta/meta.

In another aspect of the above polymer-bonded quaterrylene and/orterrylene dye, P may have one or more than one quaterrylene and/orterrylene dye molecule (e.g., 1, 2, 3, 4, 5, 6, or more quaterryleneand/or terrylene dye molecules) bonded thereto. In this regard, it is tobe noted that if two or more quaterrylene and/or terrylene dye moleculesare bonded to a polymer molecule P, the two or more dye molecules mayconsist of at least two identical or different quaterrylene dyemolecules, at least two identical or different terrylene dye molecules,and at least one quaterrylene dye molecule and at least one terrylenedye molecule. Conversely, a quaterrylene or terrylene dye molecule mayhave one or more than one polymer molecule P (e.g., 1, 2, 3, 4 or morepolymer molecules P) bonded thereto. Even further, a polymer molecule Pmay have at least two quaterrylene and/or terrylene dye molecules bondedthereto, at least one of these quaterrylene and/or terrylene dyemolecules being bonded to at least one additional polymer molecule P(which in turn may or may not be bonded to one or more additionalquaterrylene and/or terrylene dye molecules).

In yet another aspect, in the above polymer-bonded quaterrylene and/orterrylene dye molecules of formulae (IV) to (IX) R₁, R₂, and R₃ mayindependently be selected from hydrogen, C₁-C₄ alkyl, C₁-C₄ alkoxy,halogen, and SO₃H and/or the quaterrylene and/or terrylene dye moleculesmay be compounds of formulae (IV) to (IX) wherein (n+p) is 1, 2 or 3 andX represents Cl or Br, or wherein (n+p) is 0 and/or R₁ and R₂ areselected from C₁-C₄ alkyl groups. Even further, the quaterrylene and/orterrylene dye molecules may be compounds of formulae (IV) to (IX) whereR₃ represents hydrogen, or compounds of formulae (IV) to (IX) wherein R₁represents SO₃H and R₂ and R₃ represent hydrogen.

The present invention also provides a process for making apolymer-bonded quaterrylene and/or terrylene dye of any one of formulae(I) to (IX) set forth above. The process comprises contacting a compoundof formula (I′) to (IX′):

wherein R₁, R₂, R₃, X and Y are as defined above for formulae (IV′) to(IX′) and n is at least 1 and (n+p) is 1, 2, 3, 4, 5, 6, 7 or 8,with a polymer P, i.e., a polymer molecule which comprises a group thatis capable of reacting with X to replace X by a group of formula OP.

In one aspect, the process may be carried out in a polar aprotic organicsolvent in which the polymer P is soluble. For example, the polarsolvent may comprise at least one of N-methylpyrrolidone, dimethylformamide, dimethyl acetamide, and dimethylsulfoxide.

In another aspect, the process may be carried out in the presence of aninorganic base and/or a strong organic non-nucleophilic base and/or inthe presence of at least one anti-foam agent such as a polyethyleneglycol and/or a derivative thereof.

In yet another aspect of the process, about 0.5 g to about 10 g ofquaterrylene and/or terrylene dye may be employed per 100 g of polymerP. In yet another aspect of the process, from about 0.2 g to about 10 gof quaterrylene and/or terrylene dye may be employed per 100 g ofpolymer P, for example at least about 0.4 g, at least about 0.5 g, atleast about 0.6 g, at least about 0.8 g, at least about 1 g, at leastabout 2 g, at least about 5 g, or at least about 8 g of quaterryleneand/or terrylene dye per 100 g of polymer P.

The present invention also provides a printing ink composition whichcomprises a polar liquid medium that has at least one polymer-bondedquaterrylene and/or terrylene dye of the present invention as set forthabove (including the various aspects thereof) dissolved or dispersedtherein.

In one aspect, the printing ink composition may comprise from about0.01% to about 40% by weight of the at least one polymer-bondedquaterrylene and/or terrylene dye based on the total weight of thecomposition. In another aspect, the printing ink composition may furthercomprise at least one conductivity imparting substance (e.g., a salt).

The present invention also provides a marking or security feature whichis made with the printing ink composition of the present invention asset forth above (including the various aspects thereof).

In one aspect, the marking or security feature may comprise at least onepolymer-bonded quaterrylene and/or terrylene dye according to thepresent invention, e.g. a polymer-bonded quaterrylene and/or terrylenedye of formula (A) or formula (B) or formula (C) and/or of any one offormulae (I) to (IX) as set forth above (including the various aspectsthereof). In another aspect, the marking or security feature maycomprise at least one of a thread, a label, a barcode, a 2D code, apattern, indicia, and a data matrix.

The present invention also provides an article which comprises themarking or security feature of the present invention as set forth above(including the various aspects thereof).

In one aspect of the article, the marking or security feature may bepresent on the article in the form a layer. In another aspect, thearticle may be at least one of a label such as, e.g., a tax label,packaging, a can, a metal, an aluminum foil, a cartridge, a closedcartridge (e.g., a capsule) that contains, e.g., a pharmaceutical, anutraceutical, a foodstuff or a beverage (such as, e.g., coffee, tea,milk, chocolate, etc.), an article made of glass, an article made ofceramic, a banknote, a stamp, a security document, an identity card, apassport, a driver's license, a credit card, an access card, a ticketsuch as, e.g., a transportation ticket or an event ticket, a voucher, avalue document, an ink-transfer film, a reflective film, a thread, and acommercial good.

The present invention further provides a method of authenticating anarticle. The method comprises providing the article with the marking orsecurity feature of the present invention as set forth above and/or theapplication onto the article the printing ink composition of the presentinvention as set forth above.

In one aspect of the method, the article may be at least one of a taxlabel, packaging, a can, a metal, an aluminum foil, a cartridge, aclosed cartridge (e.g., a capsule) that contains, e.g., apharmaceutical, a nutraceutical, a foodstuff or a beverage (such as,e.g., coffee, tea, milk, chocolate, etc.), an article made of glass, anarticle made of ceramic, a banknote, a stamp, a security document, anidentity card, a passport, a driver's license, a credit card, an accesscard, a ticket such as, e.g., a transportation ticket or an eventticket, a voucher, a value document, an ink-transfer film, a reflectivefilm, a thread, and a commercial good.

The present invention also provides a dye-doped polymer which isobtainable by a method according to the present invention as set forthabove (including the various aspects thereof). In this polymer at leastabout 0.1% to 10% of all polymer molecules have bonded thereto aquaterrylene and/or terrylene dye.

In one aspect, the polymer may comprise a phenolic resin such as, e.g.,a phenolic resin of formula

wherein the groups R₄ may be the same or different and are selected fromalkyl groups having from 1 to about 10 carbon atoms and the averagenumber of m is from about 1 to about 30, for example, from about 1 toabout 25, from about 1 to about 15, from about 1 to about 10, from about1 to about 5, from about 1 to about 3, from about 5 to about 15, fromabout 5 to about 10, from about 10 to about 20, or from about 20 toabout 30. The groups R₄ may be the same or different (preferably thesame) and may, for example, be selected from tert-butyl, tert-octyl andbranched nonyl. Further, a group R₄ may be in the meta- or para-positionwith respect to the OH group (in formula (D) only the para position isshown), and there may be more than one group R₄ (e.g., 2 or 3 groups R₄)present on a phenyl ring. For example, if two groups R₄ are present on aphenyl ring (the same or different, preferably the same groups R₄) theymay be present in any of the available positions on the phenyl ring,such as, e.g., meta/para or meta/meta.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

The particulars shown herein are by way of example and for purposes ofillustrative discussion of the embodiments of the present invention onlyand are presented in the cause of providing what is believed to be themost useful and readily understood description of the principles andconceptual aspects of the present invention. In this regard, no attemptis made to show structural details of the present invention in moredetail than is necessary for the fundamental understanding of thepresent invention, the description making apparent to those skilled inthe art how the several forms of the present invention may be embodiedin practice.

As set forth above, the quaterrylene and/or terrylene dyes which inaccordance with the present invention are to be bonded to a polymer maybe of formulae (A) or (B) or (C):

In the above formulae (A), (B) and (C) the groups Z may represent O, Sor N—R. Additionally, the unit or units —CO—Z—CO— may independently bereplaced by a unit —CS—Z—CO—, or a unit —CS—Z—CS—, or by thecorresponding dicarboxylic acid. Further, for Z═N—R the unit —CO—Z—CO—may further be replaced by a unit of formula —C(═NR′)—NR—CO—. In thecase of formula (A) and formula (B) the two units —CO—Z—CO— may be thesame or different. If these units are different, one of the units may,for example, be —CO—O—CO— and the other one may be —CO—NR—CO—, or onemay be —CO—NR—CO— and the other one may be —C(═NR′)—NR—CO, or may be—CS—O—CS—, or one unit may be —CO—NR—CO— and the other one may be—CO—NR*—CO—, with R and R* being different from each other, etc. (R*having the same meanings as R).

The groups R and R′ in the above formulae independently represent anoptionally substituted aliphatic, cycloaliphatic, aromatic,heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkylgroup having from 1 to about 20 carbon atoms. Additionally, R and R′ maybe combined to form, together with the N atoms to which they areattached, an optionally substituted and/or fused 5- to 7-membered ring.

Regarding the meanings of the groups R, R′, R″, R₁, R₂, R₃ and R₄mentioned herein, the following applies throughout the presentspecification and the appended claims (it being understood thatthroughout the present specification and the appended claims theindicated number of carbon atoms invariably refers to the respectiveunsubstituted group):

An “optionally substituted alkyl” group includes linear and branchedalkyl groups which preferably have from 1 to about 12 carbon atoms,e.g., from 1 to about 8 carbon atoms, from 1 to about 6 carbon atoms, orfrom 1 to about 4 carbon atoms. Specific non-limiting examples thereofinclude methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,tert-butyl, sec-butyl, linear or branched pentyl (e.g., 2-methylbutyl,2-ethylpropyl and 2,2-dimethylpropyl), linear or branched hexyl (e.g.,2-ethylbutyl, 3-ethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, and2,3-dimethylbutyl), linear or branched heptyl, linear or branched octyl(e.g., 2-ethylhexyl), and linear or branched nonyl. The alkyl groups maybe substituted with one or more substituents (e.g., one, two, three,four, etc.). Non-limiting examples of these substituents include OH,halogen such as, e.g., F, Cl, Br, and I (as in, e.g., trifluoromethyl,trichloromethyl, pentafluorethyl and 2,2,2-trifluoroethyl), alkoxyhaving from 1 to about 6 carbon atoms, e.g., from 1 to about 4 carbonatoms, such as, e.g., methoxy, ethoxy, propoxy and butoxy, acyloxyhaving from 1 to about 4 carbon atoms such as, e.g., acetoxy andpropionyloxy, aryloxy having from about 6 to about 10 carbon atoms suchas, e.g., (optionally substituted) phenoxy, aroyloxy having from about 6to about 10 carbon atoms such as, e.g., benzoyloxy, —COOH (includingpartially or completely salified forms thereof), alkoxycarbonyl havingfrom 1 to about 4 carbon atoms in the alkyl groups such as, e.g.,methoxycarbonyl and ethoxycarbonyl, —SO₃H, alkylsulfonyl, arylsulfonyl,alkylsulfonylamino, nitro, cyano, amino, monoalkylamino and dialkylaminowherein the alkyl groups have from 1 to about 6 carbon atoms, e.g., from1 to about 4 carbon atoms, such as, e.g., methylamino, dimethylamino,ethylamino, diethylamino, propylamino and dipropylamino. The alkylgroups may also be substituted by one or more optionally substitutedcycloalkyl groups (preferably having from 3 to about 8 ring carbonatoms) as further set forth below. Preferred substituents for the alkylgroups include F, Cl, Br, OH, methoxy, ethoxy, —COOH, —SO₃H, amino,methylamino, ethylamino, dimethylamino and diethylamino. If more thanone substituent is present, the substituents may be the same ordifferent. Also, one or more (e.g., one or two) of the C atoms of thealkyl group may be replaced by a heteroatom such as, e.g., O, S and NR′″(with R′″ representing, for example, H or alkyl having from 1 to about 4carbon atoms). Further, the alkyl group may have one or more carbonylgroups (C═O) incorporated therein and/or may comprise one or morecarbon-carbon double and/or triple bonds (such as in, e.g., vinyl, allyland propargyl).

An “optionally substituted cycloalkyl” group preferably comprises fromabout 3 to about 12 ring carbon atoms, more preferably from about 5 toabout 8 ring carbon atoms such as, e.g., cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. The cycloalkylgroups may be substituted with one or more substituents (e.g., one, two,three, four, etc). Non-limiting examples of these substituents includeOH, halogen such as, e.g., F, Cl, Br, and I, alkoxy having from 1 toabout 6 carbon atoms, e.g., from 1 to about 4 carbon atoms, such as,e.g., methoxy, ethoxy, propoxy and butoxy, acyloxy having from 1 toabout 4 carbon atoms such as, e.g., acetoxy and propionyloxy, aryloxyhaving from about 6 to about 10 carbon atoms such as, e.g., (optionallysubstituted) phenoxy, aroyloxy having from about 6 to about 10 carbonatoms such as, e.g., benzoyloxy, —COOH (including partially orcompletely salified forms thereof), alkoxycarbonyl having from 1 toabout 4 carbon atoms in the alkyl groups such as, e.g., methoxycarbonyland ethoxycarbonyl, —SO₃H, alkylsulfonyl, arylsulfonyl,alkylsulfonylamino, nitro, cyano, amino, monoalkylamino and dialkylaminowherein the alkyl groups have from 1 to about 6 carbon atoms, e.g., from1 to about 4 carbon atoms, such as, e.g., methylamino, dimethylamino,ethylamino, diethylamino, propylamino and dipropylamino. The cycloalkylgroups may also be substituted by one or more optionally substitutedalkyl groups (preferably having from 1 to about 4 carbon atoms) as setforth above. Preferred substituents for the alkyl groups include F, Cl,Br, OH, methoxy, ethoxy, —COOH, —SO₃H, amino, methylamino, ethylamino,dimethylamino and diethylamino. If more than one substituent is present,the substituents may be the same or different. Further, the cycloalkylgroup may have one or more carbonyl groups (C═O) incorporated thereinand/or may comprise one or more carbon-carbon double bonds (such as in,e.g., cyclopentenyl and cyclohexenyl).

An “optionally substituted aryl” group and an “optionally substitutedheteroaryl” group denote optionally fused aryl and heteroaryl groupswhich preferably comprise from about 5 to about 15 ring members, e.g.,from about 6 to about 10 ring members. The heteroaryl groups willusually comprise from 1 to about 3 ring members selected from O, S and Nand may be partially or fully hydrogenated. Specific examples of thesearyl and heteroaryl groups include phenyl, naphthyl, anthranyl,phenanthryl, 2- or 3-furyl, 2- or 3-thienyl, 1-, 2- or 3-pyrrolyl, 1-,2-, 4- or 5-imidazolyl, 1-, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5-oxazolyl,3-, 4- or 5-isoxazolyl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5-isothiazolyl,2-, 3- or 4-pyridyl, 2-, 4-, 5- or 6-pyrimidinyl, 1,2,3-triazol-1-, -4-or -5-yl, 1,2,4-triazol-1-, -3- or -5-yl, 1- or 5-tetrazolyl,1,2,3-oxadiazol-4- or -5-yl, 1,2,4-oxadiazol-3- or -5-yl,1,3,4-thiadiazol-2- or -5-yl, 1,2,4-thiadiazol-3- or -5-yl,1,2,3-thiadiazol-4- or -5-yl, 3- or 4-pyridazinyl, pyrazinyl, 1-, 2-,3-, 4-, 5-, 6- or 7-indolyl, indazolyl, 4- or 5-isoindolyl, 1-, 2-, 4-or 5-benzimidazolyl, 1-, 3-, 4-, 5-, 6- or 7-benzopyrazolyl, 2-, 4-, 5-,6- or 7-benzoxazolyl, 3-, 4-, 5-, 6- or 7-benzisoxazolyl, 2-, 4-, 5-, 6-or 7-benzothiazolyl, 2-, 4-, 5-, 6- or 7-benzisothiazolyl, 4-, 5-, 6- or7-benz-2,1,3-oxadiazolyl, 2-, 3,4-, 5-, 6-, 7- or 8-quinolyl, 1-, 3-,4-, 5-, 6-, 7- or 8-isoquinolyl, 3-, 4-, 5-, 6-, 7- or 8-cinnolinyl, 2-,4-, 5-, 6-, 7- or 8-quinazolinyl, 5- or 6-quinoxalinyl, 2-, 3-, 5-, 6-,7- or 8-2H-benzo-1,4-oxazinyl, 1,3-benzodioxol-5-yl,1,4-benzo-dioxane-6-yl, 2,1,3-benzothiadiazol-4- or -5-yl or2,1,3-benzoxadiazol-5-yl, 2,3-dihydro-2-, -3-, -4- or -5-furyl,2,5-dihydro-2-, -3-, -4- or -5-furyl, tetrahydro-2- or -3-furyl,1,3-dioxolan-4-yl, tetrahydro-2- or -3-thienyl, 2,3-dihydro-1-, -2-,-3-, 4- or -5-pyrrolyl, 2,5-dihydro-1-, -2-, -3-, -4- or -5-pyrrolyl,1-, 2- or 3-pyrrolidinyl, tetrahydro-1-, -2- or -4-imidazolyl,2,3-dihydro-1-, -2-, -3-, -4- or -5-pyrazolyl, tetrahydro-1-, -3- or-4-pyrazolyl, 1,4-dihydro-1-, -2-, -3- or -4-pyridyl,1,2,3,4-tetrahydro-1-, -2-, -3-, -4-, -5- or -6-pyridyl, 1-, 2-, 3- or4-piperidinyl, 2-, 3- or 4-morpholinyl, tetrahydro-2-, -3- or-4-pyranyl, 1,4-dioxaneyl, 1,3-dioxane-2-, -4- or -5-yl, hexahydro-1-,-3- or -4-pyridazinyl, hexahydro-1-, -2-, -4- or -5-pyrimidinyl, 1-, 2-or 3-piperazinyl, 1,2,3,4-tetrahydro-1-, -2-, -3-, -4-, -5-, -6-, -7- or-8-quinolyl, 1,2,3,4-tetrahydro-1-, -2-, -3-, -4-, -5-, -6-, -7- or-8-isoquinolyl, 2-, 3-, 5-, 6-, 7- or8-3,4-dihydro-2H-benzo-1,4-oxazinyl, 2,3-methylenedioxyphenyl,3,4-methylenedioxyphenyl, 2,3-ethylenedioxyphenyl,3,4-ethylenedioxyphenyl, 3,4-(difluoromethylenedioxy)phenyl,2,3-dihydrobenzofuran-5- or -6-yl, 2,3-(2-oxomethylenedioxy)phenyl,3,4-dihydro-2H-1,5-benzodioxepin-6- or -7-yl, 2,3-dihydrobenzofuranyl,2,3-dihydro-2-oxofuranyl. The aryl and heteroaryl groups may besubstituted with one or more (e.g., one, two, three, four, etc.)substituents which are preferably selected from halogen such as, e.g.,F, Cl, Br, and I, OH, —COOH (including partially or completely salifiedforms thereof), —SO₃H, nitro, cyano, alkoxy having from 1 to about 4carbon atoms such as, e.g., methoxy and ethoxy, aryloxy having from 1 toabout 4 carbon atoms such as, e.g., acetoxy and propionyloxy, aryloxyhaving from about 6 to about 10 carbon atoms such as, e.g., phenoxy,aroyloxy having from about 6 to about 10 carbon atoms such as, e.g.,benzoyloxy, amino, monoalkylamino and dialkylamino wherein the alkylgroups have from 1 to about 6 carbon atoms, e.g., from 1 to about 4carbon atoms, such as, e.g., methylamino, dimethylamino, ethylamino,diethylamino, propylamino and dipropylamino, acylamino having from 1 toabout 8 carbon atoms such as, e.g., acetylamino and propionylamino,aminocarbonyl, monoalkylaminocarbonyl, diaminocarbonyl andalkoxycarbonyl having from 1 to about 4 carbon atoms in the alkyl groupssuch as, e.g., methoxycarbonyl and ethoxycarbonyl, optionallysubstituted acyl having from 2 to about 8 carbon atoms such as acetyland propionyl, alkylsulfonyl, arylsulfonyl and alkylsulfonylamino. Ifmore than one substituent is present, the substituents may be the sameor different. Also, the aryl and heteroaryl groups may be substituted byaryl groups and/or alkylaryl groups. Specific and non-limiting examplesof substituted aryl groups include chlorophenyl, dichlorophenyl,fluorophenyl, bromophenyl, phenoxyphenyl, hydroxyphenyl,dihydroxyphenyl, methoxyphenyl, aminophenyl, dimethylaminophenyl andbiphenylyl.

An “optionally substituted alkylaryl” group and an “optionallysubstituted alkylheteroaryl” group denote optionally substituted arylgroups and optionally substituted heteroaryl groups as set forth abovewhich are (further) substituted by at least one optionally substitutedalkyl group (preferably comprising from 1 to about 6, e.g., from 1 toabout 4 carbon atoms) as set forth above. Specific examples thereofinclude tolyl, xylyl, mesityl, ethylphenyl, cumyl, trifluormethylphenyl,hydroxytolyl, chlorotolyl, methylpyridyl, methylfuryl, methylthienyl,diisopropylphenyl, di(tert-butyl)phenyl, and methylnaphthyl.

An “optionally substituted arylalkyl” group and an “optionallysubstituted heteroarylalkyl” group denote optionally substituted alkylgroups (preferably comprising from 1 to about 6, e.g., from 1 to about 4carbon atoms) as set forth above which are (further) substituted by atleast one optionally substituted aryl group and/or optionallysubstituted heteroaryl group as further set forth above. Specificexamples thereof include benzyl, methylbenzyl, chlorobenzyl,dichlorbenzyl, hydroxybenzyl, 1-phenylethyl, 2-phenylethyl,pyridylmethyl, thienylmethyl, furylmethyl, and naphthylmethyl.

An “optionally substituted and/or fused 5- to 7-membered ring” denotes asaturated, partially unsaturated or aromatic N-heterocyclic ring whichin addition to the one or two N atoms already present therein maycomprise one or two additional heteroatoms which are selected from O, Nand S. The ring will usually have five or six ring members. Also, thering will often comprise no additional heteroatom. Further, the ring mayhave one or two aromatic and/or heteroaromatic rings (e.g., benzenerings) fused to it and/or may be substituted with one or more (e.g.,one, two, three, four, etc.) substituents which are preferably selectedfrom F, Cl, Br, and I, OH, —COOH (including partially or completelysalified forms thereof), —SO₃H, cyano, nitro, alkoxy having from 1 toabout 4 carbon atoms such as, e.g., methoxy and ethoxy, acyloxy havingfrom 1 to about 4 carbon atoms such as, e.g., acetoxy and propionyloxy,aryloxy having from about 6 to about 10 carbon atoms such as, e.g.,phenoxy, aroyloxy having from about 6 to about 10 carbon atoms such as,e.g., benzoyloxy, amino, monoalkylamino and dialkylamino wherein thealkyl groups have from 1 to about 6 carbon atoms, e.g., from 1 to about4 carbon atoms, such as, e.g., methylamino, dimethylamino, ethylamino,diethylamino, propylamino and dipropylamino, acylamino having from 1 toabout 8 carbon atoms such as, e.g., acetylamino and propionylamino,aminocarbonyl, monoalkylaminocarbonyl, diaminocarbonyl andalkoxycarbonyl having from 1 to about 4 carbon atoms in the alkyl groupssuch as, e.g., methoxycarbonyl and ethoxycarbonyl, optionallysubstituted acyl having from 2 to about 8 carbon atoms such as acetyland propionyl, alkylsulfonyl, arylsulfonyl and alkylsulfonylamino,optionally substituted alkyl having from 1 to about 6 carbon atoms suchas, e.g., methyl, ethyl, hydroxymethyl and hydroxyethyl, optionallysubstituted (hetero)aryl such as, e.g., phenyl, tolyl, xylyl,hydroxyphenyl, pyridinyl and pyrrolyl, and optionally substitutedalkylaryl such as, e.g., benzyl. If more than one substituent ispresent, the substituents may be the same or different. Non-limitingexamples of unsubstituted N-containing 5- to 7-membered rings includepyrrolyl, pyrrolidinyl, pyridinyl, pyrimidinyl, piperidinyl,morpholinyl, piperazinyl, thienyl, pyrazolyl, pyrazolidinyl, oxazolyland oxazolidinyl

Preferred halogens as meaning for X in the above formulae (A) to (C) areCl and Br, although F and I are suitable as well.

Regarding the values for n and p in the above formulae (A) to (C) it isto be noted that the value of (n+p) will often be not higher than 8,e.g., not higher than 7, or not higher than 6, with n and p eachpreferably having a value of 0, 1, 2, 3 4, 5 6 7 or 8. Further, thevalue of p will often be 0. If n equals 0, at least one of R, R′ and R″comprises at least one group X as substituent. In the latter case oftenonly one group X will be present in R, R′ or R″, although it is entirelypossible for two, three or more groups X to be present in R and/or R′and/or R″.

If two or more groups X are present in compounds of formulae (A), (B)and (C) they may be the same or different (and preferably are the same)and may be present as substituents on the quaterrylene and/or terryleneskeleton and/or be a part of one or more of R, R′ and R″. However, iftwo or more groups X are present they will preferably be present eitheras substituents on the quaterrylene and/or terrylene skeleton or as apart of R and/or R′.

By way of non-limiting example and also as a preferred embodiment,compounds of general formula (IV to IX) set forth above includecompounds wherein n=p=0, R₁═H, R₂═R₃═C₁₋₄ alkyl (e.g., C₃ alkyl such asisopropyl), and P represents a group derived from a phenolic resin ofgeneral formula (D) wherein m=1 to 4 and the groups R₄ are preferablyidentical and represent C₁₋₁₀ alkyl groups (e.g., C₄ alkyl such astert.-butyl); compounds of general formula (IV to IX) set forth aboveinclude compounds wherein n=p=0, R₁═R₂═C₁₋₄ alkyl (e.g., C₃ alkyl suchas isopropyl or C₄ alkyl such as tert.-butyl), and P represents a groupderived from a phenolic resin of general formula (D) wherein m=1 and thegroups R₄ are preferably identical and represent C₁₋₁₀ alkyl groups(e.g., C₄ alkyl such as tert.-butyl); and compounds of general formulae(I to III) set forth above include compounds wherein n=0 or 3, p=0, forn=3, X=halogen (such as Cl or Br), the groups Z are identical (if twogroups Z are present) and represent N—R, with R being an alkylarylgroup, e.g., a dialkylphenyl group wherein the two alkyl groups arepreferably identical and represent C₁₋₄ alkyl groups (e.g., C₃ alkylsuch as isopropyl), and P represents a group derived from a phenolicresin of general formula (D) wherein m=1 and the groups R₄ arepreferably identical and represent C₁₋₁₀ alkyl groups (e.g., C₄ alkylsuch as tert.-butyl).

According to the method of the present invention the solubility and/orthe dispersibility of a quaterrylene and/or terrylene dye in a liquidmedium is increased by (preferably covalently) binding the quaterryleneand/or terrylene dye to a (at least one) polymer that is soluble in theliquid medium. The term “soluble in the liquid medium” means that thepolymer shows a more than negligible solubility in the liquid medium,such as, e.g., a solubility of at least about 0.2 g of polymer per 100 gof liquid medium, preferably at least about 1 g, e.g., at least about 2g, at least about 5 g, or at least about 10 g of polymer per 100 g ofliquid medium. If the liquid medium is a polar liquid medium (as it isoften encountered in printing inks) the polymer may comprise at leastone (recurring) monomer unit that comprises at least one polar groupwhich may, for example, be selected from hydroxy, carboxy and aminogroups. Accordingly, the polymer may, for example, comprise a phenolicresin such as, e.g., a novolac resin or any other kind of phenolformaldehyde condensation product. For example, the phenolic resin maybe or include a phenolic resin of formula

wherein the groups R₄ may be the same or different and are selected from(optionally substituted) alkyl groups having from 1 to about 10 carbonatoms and the average number of m is from about 1 to about 30, forexample, from about 1 to about 25, from about 1 to about 15, from about1 to about 10, from about 1 to about 5, from about 1 to about 3, fromabout 5 to about 15, from about 5 to about 10, from about 10 to about20, or from about 20 to about 30. The groups R₄ may be the same ordifferent (preferably the same) and may, for example, be selected fromtert-butyl, tert-octyl and branched nonyl. Further, a group R₄ may be inthe meta- or para-position with respect to the OH group (in formula (D)only the para position is shown), and there may be more than one groupR₄ (e.g., 2 or 3 groups R₄) present on a phenyl ring. For example, iftwo groups R₄ are present on a phenyl ring (the same or different,preferably the same groups R₄) they may be present in any of theavailable positions on the phenyl ring, such as, e.g., meta/para ormeta/meta with respect to the OH group.

Regarding formula (D), it is to be appreciated that each of the phenylrings comprised therein may comprise 1 or 2 additional substituents.These substituents may, for example, be additional optionallysubstituted alkyl groups (preferably having from 1 to about 10 carbonatoms), halogen such as, e.g., F, Cl and Br, OH, COOH, and amino. Ifadditional substituents are present they may be the same or different.

The average value of m in the above formula (D) will often be at leastabout 1, at least about 2, e.g., at least about 3, or at least about 4,and will also often be not higher than about 20, e.g., not higher thanabout 15, or not higher than about 10.

The weight ratio of quaterrylene and/or terrylene dye to polymer(s) thatis employed in the method of the present invention depends on severalfactors such as, e.g., the molecular weights of the quaterrylene and/orterrylene dyes and the polymer(s), the average number of quaterryleneand/or terrylene dye molecules that are to be bonded to the a singlepolymer molecule or the average number of polymer molecules that are tobe bonded to a single quaterrylene or terrylene dye molecule. Inparticular, in a polymer-bonded quaterrylene and/or terrylene dye of thepresent invention a single polymer molecule P may have one or more thanone quaterrylene and/or terrylene dye molecule (e.g., an average of 1,2, 3, 4, 5, 6, or more quaterrylene and/or terrylene dye molecules)bonded thereto. Conversely, a quaterrylene and/or terrylene dye moleculemay have one or more than one polymer molecule P (e.g., an average of 1,2, 3, 4, or more polymer molecules P) bonded thereto. Even further, apolymer molecule P may have at least two quaterrylene and/or terrylenedye molecules bonded thereto, at least one of these quaterrylene and/orterrylene dye molecules being bonded to at least one additional polymermolecule P (which in turn may or may not be bonded to one or moreadditional quaterrylene and/or terrylene dye molecules). As noted above,if two of more dye molecules are bonded to a polymer molecule P, theymay be identical or different, i.e., the same or different quaterrylenemolecules, the same of different terrylene molecules, at least onequaterrylene molecule and at least one terrylene molecule. Of course,mixtures of polymer molecules which are different in terms of the numberand/or type of dye molecules bonded thereto are also within the scope ofthe present invention.

It is further possible (and sometimes preferred) to employ a relativelylarge stoichiometric excess of polymer(s) with respect to quaterryleneand/or terrylene dye. This will result in a polymer wherein only a smallfraction (e.g., not more than about 0.1%, not more than about 0.5%, notmore than about 1%, or not more than about 2%, not more than about 4%,not more than about 6%, not more than about 8%, not more than about 10%)of the polymer molecules has at least one quaterrylene and/or terrylenedye molecule bonded thereto, thereby affording a quaterrylene and/orterrylene dye-doped polymer of the present invention. The quaterryleneand/or terrylene dye-doped polymer can be used for the same purposes forwhich the polymer-bonded quaterrylene and/or terrylene dye of thepresent invention is employable such as, e.g., as a component of aprinting ink composition.

By way of non-limiting example, in the process for making thepolymer-bonded quaterrylene and/or terrylene dyes of formulae (I) to(IX) set forth above it is preferred to use about 0.5 g to about 10 g ofquaterrylene and/or terrylene dye per 100 g of polymer such as, e.g.,phenolic resin. In particular, it will often be advantageous to employat least about 0.8 g, e.g., at least about 1 g, but not more than about5 g, e.g., not more than about 3 g, or not more than about 2 g ofquaterrylene and/or terrylene dye per 100 g of polymer.

It is, of course, possible to react one quaterrylene and/or terrylenedye with more than one or more than one type of polymer. By way ofnon-limiting example, one or more quaterrylene and/or terrylene dyes ofthe above formulae (A) or (B) or (C) may be reacted with a mixture ofpolymers of the above formula (D). Conversely, two or more differentquaterrylene and/or terrylene dyes may be reacted with (bonded to) asingle (type of) polymer. Finally, two or more different quaterryleneand/or terrylene dyes may be reacted with two or more different (typesof) polymers, although this will usually result in difficult to controlreaction mixtures.

The reaction conditions which are required or advantageous, respectivelyfor the reaction between a quaterrylene and/or terrylene dye and apolymer to which the former is to be bonded depend on many factors suchas, e.g., the groups that are to participate in the reaction and anyother (reactive) groups that may be present in the quaterrylene and/orterrylene dye and/or the polymer. Reaction conditions which are suitablefor a specific pair of reactive groups in the quaterrylene and/orterrylene dye and in the polymer are well known to those of skill in theart. For example, especially in cases where a nucleophilic substitutionis involved it will often be beneficial to carry out the reaction in anaprotic polar organic solvent such as, e.g., N-methylpyrrolidone (NMP),dimethyl formamide, dimethyl acetamide, and dimethylsulfoxide or amixture of two or more thereof, and in the presence of an inorganic orstrong non-nucleophilic organic base. Examples of inorganic and organicbases suitable for catalyzing nucleophilic substitution reactions arewell known to those of skill in the art. An example of a suitableinorganic base is K₂CO₃. Reaction temperatures will often range fromabout 50° C. to about 140° C., also depending on the boiling point ofthe solvent used. It further will often be desirable to employ ananti-foam agent such as, e.g., a polyethylene glycol or derivativethereof. The reaction product (polymer-bonded quaterrylene and/orterrylene dye) can usually be isolated from the resultant reactionmixture and optionally purified by conventional means such as, e.g.,filtration, centrifugation, extraction, chromatographic methods, etc.

Typical (non-limiting) reactions between a quaterrylene and/or terrylenedye and a polymer (phenolic resin) in accordance with the processes ofthe present invention are represented below:

In this regard, it is to be appreciated that in the presentspecification and the appended claims the letter “P” is used to denotetwo different entities: in one case an unreacted polymer and in theother case the polymer in which one or more groups thereof have reactedwith one or more corresponding groups of one or more quaterrylene and/orterrylene dye molecules to form a (preferably covalent) linkage betweenthe remainder of the polymer and the remainder of the quaterryleneand/or terrylene dye.

A printing ink composition in accordance with the present inventioncomprises a (preferably polar) liquid medium and one or more (types of)polymer-bonded quaterrylene and/or terrylene dyes as set forth above(e.g., a mixture of two or three different quaterrylene and/or terrylenedyes, all bonded to the same type of polymer, or bonded to more than onetype of polymer) dissolved or dispersed in the medium. The concentrationof the polymer-bonded quaterrylene and/or terrylene dye(s) in the mediumdepends on several factors such as, e.g., the polymer(s) to which thequaterrylene and/or terrylene dye(s) is/are bonded, the desired colorintensity, the liquid medium, the remaining (optional) components of thecomposition, the intended purpose of the printing ink composition, andthe substrate onto which the printing ink composition is to be applied.Often the (total) concentration of the one or more polymer-bondedquaterrylene and/or terrylene dyes in the printing ink composition willbe at least about 0.01%, at least about 0.02%, or at least 0.05% byweight, and will usually be not higher than about 40% by weight, e.g.not higher than about 20%, not higher than about 10%, or not higher thanabout 5% by weight based on the total weight of the composition.

The intended purpose of the printing ink composition is one of severalfactors which determines suitable and desirable concentration ranges forthe polymer-bonded quaterrylene and/or terrylene dye(s) as well as thetypes and concentration ranges of suitable or desirable optionalcomponents of the composition. There are many different types ofprinting processes. Non-limiting examples thereof include inkjetprinting (thermal, piezoelectric, continuous, etc.), flexography,intaglio printing (e.g., gravure printing), screen printing, letterpressprinting, offset printing, pad printing, relief printing, planographicprinting and rotogravure printing. In a preferred embodiment, a printingink composition in accordance with the present invention is suitable (atleast) for inkjet printing. Industrial inkjet printers, commonly usedfor numbering, coding and marking applications on conditioning lines andprinting presses, are particularly suitable. Preferred ink jet printersinclude single nozzle continuous ink jet printers (also called raster ormulti level deflected printers and drop-on-demand ink-jet printers, inparticular valve jet printers.) Accordingly, the following discussion ofprinting ink compositions relates primarily to compositions for inkjetprinting. However, it is to be kept in mind that the present inventionis not limited to printing ink compositions for inkjet printing butrather encompasses all printing ink compositions in which quaterryleneand/or terrylene dyes can be employed. Accordingly, the followingconsiderations and statements apply mutatis mutandis to all printing inkcompositions in which the polymer-bonded quaterrylene and/or terrylenedyes in accordance with the teaching of the present invention areuseful.

Printing inks in general comprise coloring agents and liquid vehicleswhich comprise solutions of resinous binders in solvents. The specificchoice of binders and solvents depends on several factors, such as, forexample, the polymer-bonded quaterrylene and/or terrylene dye(s), theremaining components that are to be present, and the nature of thesubstrate to be printed. Non-limiting examples of suitable binders foruse in the ink compositions for inkjet printing include binders whichare conventionally used in inkjet printing inks, including resins suchas nitrocellulose, acrylate resins and polyester resins (such as, e.g,DYNAPOL® L 1203, L 205, L 206, L 208, L 210, L 411, L 651, L658, L 850,L 912, L 952, LH 530, LH 538, LH 727, LH 744, LH 773, LH 775, LH 818, LH820, LH 822, LH 912, LH 952, LH 530, LH 538, LH 727, LH 744, LH 773, LH775, LH 818, LH 820, LH 822, LH 823, LH 826, LH 828, LH 830, LH 831, LH832, LH 833, LH 838, LH898, LH 908, LS436, LS615, P1500, S1218, S1227,S1247, S1249, S1252, S1272, S1401, S1402, S1426, S1450, S1510, S1606,S1611, S243, S320, S341, S361, S394, and S EP1408 from Evonik). Ofcourse, other suitable resins known to those of skill in the art may beused as well. A typical (total) concentration of the one or more bindersin the printing ink composition is from about 0.5% to about 10% byweight, based on the total weight of the composition. In this regard, itfurther is to be taken into account that typical viscosity values forinkjet printing inks are in the range of from about 4 to about 30 mPa·sat 25° C.

It further is to be appreciated that the polymer which has one or morequaterrylene and/or terrylene dye molecules bonded thereto (and in thecase of the quaterrylene and/or terrylene dye-doped polymer of thepresent invention as set forth above, also the polymer which is notbonded to any quaterrylene and/or terrylene dye molecule but is presentin admixture with polymer that has quaterrylene and/or terrylene dyebonded thereto) may also act as a binder for the composition. At anyrate, the (principal) binder of the ink composition must be compatiblewith the polymer which a quaterrylene and/or terrylene dye bondedthereto, e.g., must not result in the formation of any insolublesubstance, etc. when combined with the latter.

Suitable solvents for inkjet printing inks are known to those of skillin the art. Non-limiting examples thereof include low-viscosity,slightly polar and aprotic organic solvents, such as, e.g., methyl ethylketone (MEK), acetone, ethyl acetate, ethyl 3-ethoxypropionate, tolueneand mixtures of two or more thereof.

In particular if the printing ink composition of the present inventionis to be applied by continuous inkjet printing the composition willusually also comprise at least one conductivity imparting agent (forexample, a salt). The conductivity imparting agent will have anon-negligible solubility in the composition. Non-limiting examples ofsuitable conductivity imparting agents include salts such as, e.g.,tetraalkyl ammonium salts (e.g., tetrabutyl ammonium nitrate, tetrabutylammonium perchlorate and tetrabutyl ammonium hexafluorophosphate),alkali metal thiocyanates such as potassium thiocyanate, alkalipotassium salts such as KPF₆ and alkali metal perchlorates such aslithium perchlorate. The conductivity imparting agent will be present ina concentration which is sufficient to provide the conductivity which isrequired or desirable. Of course, mixtures of two or more differentconductivity imparting agents (salts) can be used. Often the one or moreconductivity imparting agents will be present in a total concentrationof from about 0.1% to 2% by weight, based on the total weight of thecomposition.

The printing ink composition according to the present invention mayfurthermore comprise one or more customary additives, such as, forexample, fungicides, biocides, surfactants, sequestering agents, pHadjusters, etc. in the amounts customary for these additives. Further,the printing ink composition may comprise one or more additionalcolorants and/or components which impart a specific optical property(i.e., components which are different from the polymer-bondedquaterrylene and/or terrylene dyes of the present invention). Theseadditional components may be selected from, for example, conventionalpigments and dyes, luminescent (e.g., fluorescent) pigments and dyes andcholesteric or nematic liquid crystals. Examples of luminescent pigmentsinclude certain classes of inorganic compounds such as the sulphides,oxysulphides, phosphates, vanadates, garnets, spinels, etc. ofnon-luminescent cations, which are doped with at least one luminescenttransition-metal or rare-earth metal cation. In order to strengthen thesecurity of the ink composition the composition may further comprise oneor more pigments and/or dyes which absorb in the visible or invisibleregion of the electromagnetic spectrum and/or may further comprise oneor more pigments and/or dyes which are luminescent. Non-limitingexamples of suitable pigments and/or dyes which absorb in the visible orinvisible region of the electromagnetic spectrum include phthalocyaninederivatives. Non-limiting examples of suitable luminescent pigmentsand/or dyes include lanthanide derivatives. The presence of pigment(s)and/or dye(s) will enhance and reinforce the security of the markingagainst counterfeiting.

The substrate or article which is to be provided with a marking and/orsecurity feature in accordance with the present invention is notparticularly limited and can be of various types. The substrate orarticle may, for example, consist (essentially) of or comprise one ormore of a metal (for example, in the form of a container such as a canfor holding various items such as, e.g., beverages or foodstuffs),optical fibers, a woven, a coating, and equivalents thereof, a plasticmaterial, a ceramic material, glass (for example, in the form of acapsule or container such as a bottle for holding various items such as,e.g., beverages or foodstuffs), cardboard, packaging, paper, and apolymeric material. It is pointed out that these substrate materials aregiven exclusively for exemplifying purposes, without restricting thescope of the invention.

The substrate may furthermore already carry at least one marking orsecurity element which comprises a substance selected from, e.g.,inorganic luminescent compounds, organic luminescent compounds,IR-absorbers, magnetic materials, forensic markers, and combinationsthereof. The marking or security element can be present in the form ofindicia or a data matrix. on the substrate surface or be incorporated(embedded) in the substrate itself. The marking can be present also inthe form of a cloud of dots or a specific pattern visible and/orinvisible to the naked eye, randomly or not distributed in the item orarticle or goods or security documents or what is described in theparagraph [0074] or [0075] it is intended to protect and/orauthenticate.

EXAMPLES

The following examples illustrate general procedures for makingpolymer-bonded quaterrylene and for terrylene dyes according to thepresent invention.

Example 1

Under an inert gas atmosphere 1.4 g of K₂CO₃ was added to a solution of10 g of phenol formaldehyde resin and 0.68 g of PEG 500 in 62.5 ml ofNMP. The resultant mixture was heated for about 1 hour at 120° C. Then0.20 g of trichloro-quaterrylene or tetrabromo-quaterrylene of the aboveformula (A) was added to the mixture, whereafter heating at 120° C. wascontinued for about 2 to about 5 hours. Following the completion of thereaction about half of the volume of the NMP was distilled off. Thereaction mixture was allowed to cool to room temperature and thereafterpoured into 33 g of iced water to which 2 ml of conc. HCl had beenadded. The resultant precipitate was filtered off and washed 3 timeswith water and then dried. This afforded about 10 g of crude powdercomprising polymer-bonded quaterrylene dye.

The crude powder was used without further purification in the followingink formulations for ink-jet printing.

Example 2

Under an inert gas atmosphere 1.4 g of K₂CO₃ was added to a solution of10 g of phenol formaldehyde resin and 0.68 g of PEG 500 in 62.5 ml ofNMP. The resultant mixture was heated for about 1 hour at 120° C. Then0.15 g of tetrabromo-terrylene or trichloro-terrylene of the aboveformula (B) was added to the mixture, whereafter heating at 120° C. wascontinued for about 2 to about 5 hours. Following the completion of thereaction about half of the volume of the NMP was distilled off. Thereaction mixture was allowed to cool to room temperature and thereafterpoured into 33 g of iced water to which 2 ml of conc. HCl had beenadded. The resultant precipitate was filtered off and washed 3 timeswith water and then dried. This afforded about 10 g of crude powdercomprising polymer-bonded terrylene dye.

The crude powder was used without further purification in the followingink formulations for ink-jet printing.

Here is disclose some ink formulation which can be used in order toobtain the marking according to the present invention.

Ink Formulation 1

Component Function % b.w. Nitrocellulose Binder resin 1.5 LithiumPerchlorate Salt for conductivity 0.5 Polymer-bonded Dye 1.0Quaterrylene Dye Acetone Solvent 97.0Ink Formulation 2

Component Function % b.w. Dynapol L411 Binder resin 1.5 (Polyesterresin) Lithium Perchlorate Salt for conductivity 0.3 Polymer-bonded Dye0.8 Quaterrylene Dye Methyl ethyl ketone Solvent 97.4Ink Formulation 3

Component Function % b.w. Dynapol L411 Binder resin 1.5 (Polyesterresin) Lithium Perchlorate Salt for conductivity 0.3 Polymer-bonded Dye2.2 Quaterrylene Dye Black Microlith ® Pigment 1.0 Methyl ethyl ketoneSolvent 95Ink Formulation 4

Component Function % b.w. Nitrocellulose Binder resin 1.5 LithiumPerchlorate Salt for conductivity 0.5 Polymer-bonded Terrylene Dye 1.0Dye Acetone Solvent 97.0Ink Formulation 5

Component Function % b.w. Dynapol L411 Binder resin 1.5 (Polyesterresin) Lithium Perchlorate Salt for conductivity 0.3 Polymer-bondedTerrylene Dye 0.8 Dye Methyl ethyl ketone Solvent 97.4Ink Formulation 6

Component Function % b.w. Dynapol L411 Binder resin 1.5 (Polyesterresin) Lithium Perchlorate Salt for conductivity 0.3 Polymer-bondedTerrylene Dye 2.2 Dye Black Microlith ® Pigment 1.0 Methyl ethyl ketoneSolvent 95

It is noted that the foregoing examples have been provided merely forthe purpose of explanation and are in no way to be construed as limitingof the present invention. While the present invention has been describedwith reference to an exemplary embodiment, it is understood that thewords which have been used herein are words of description andillustration, rather than words of limitation. Changes may be made,within the purview of the appended claims, as presently stated and asamended, without departing from the scope and spirit of the presentinvention in its aspects. Although the present invention has beendescribed herein with reference to particular means, materials andembodiments, the present invention is not intended to be limited to theparticulars disclosed herein; rather, the present invention extends toall functionally equivalent structures, methods and uses, such as arewithin the scope of the appended claims.

What is claimed:
 1. A method of increasing at least one of thesolubility and dispersibility of a quaterrylene and/or terrylene dye ina liquid medium, wherein the method comprises directly covalentlybinding or through a bridging group the quaterrylene or terrylene dye toa polymer which is soluble in the liquid medium.
 2. The method of claim1, wherein the polymer comprises a phenolic resin of formula

wherein the groups R₄ may be the same or different and are selected fromalkyl groups having from 1 to about 10 carbon atoms and the averagenumber of m is from about 1 to about
 30. 3. The method of claim 1,wherein the quaterrylene or terrylene dye is a compound of formula (A),(B) or (C):

wherein the groups Z, the same or different from each other, representO, S or N—R, provided that in the above formulae the unit —CO—Z—CO— (inthe case of formula (A) or formula (B) one or both units of formula—CO—Z—CO—) may be replaced by a unit —CS—Z—CO—, or a unit —CS—Z—CS—, orby [—COOH HOOC—] (i.e., the dicarboxylic acid instead of the cyclicanhydride) and further provided that for Z═N—R a unit —CO—Z—CO— may bereplaced by a unit of formula —C(═NR′)—NR—CO—; R and R′ independentlyrepresent an optionally substituted aliphatic, cycloaliphatic, aromatic,heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkylgroup having from 1 to about 20 carbon atoms; and R and R′ may becombined to form, together with the N atoms to which they are attached,an optionally substituted and/or fused 5- to 7-membered ring; the groupsX may be the same or different and represent halogen, isocyanate andCOOH; the groups Y may be the same or different and are selected fromOH, NO₂, CN, groups of formula R″, OR″, COOR″, OCOR″, CONHR″, CON(R″)₂,OCONHR″, OCON(R″)₂, COR″, SO₃H, SO₃R″, SO₂NHR″, SO₂N(R″)₂, NHCOR″,NRCOR″, NHCOOR″, NRCOOR″, NHSO₂R″, NRSO₂R″, NHR″, and N(R″)₂, whereinthe groups R″ may be the same or different and represent an optionallysubstituted aliphatic, cycloaliphatic, aromatic, heteroaromatic,alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkyl group havingfrom 1 to about 20 carbon atoms and may also be combined to form,together with the N atom to which they are attached, an optionallysubstituted and/or fused 5- to 7-membered ring; n and p each represent 0or an integer of from 1 to 8, provided that (n+p) is not higher than 8and further provided that for n=0 at least one of R, R′ and R″ comprisesat least one group X as substituent.
 4. A quaterrylene or terrylene dyewhose solubility or dispersibility in a polar liquid medium has beenincreased by having been directly covalently bonded or though a bridginggroup to a polymer.
 5. A polymer-bonded quaterrylene or terrylene dye offormula (A), (B) or (C):

wherein the groups Z, the same or different from each other, representO, S or N—R, provided that in the above formulae the unit —CO—Z—CO—(inthe case of formula (A) or formula (B) one or both units of formula—CO—Z—CO—) may be replaced by a unit —CS—Z—CO—, or a unit —CS—Z—CS—, orby [—COOH HOOC—] (i.e., the dicarboxylic acid instead of the cyclicanhydride) and further provided that for Z═N—R a unit —CO—Z—CO-may bereplaced by a unit of formula —C(═NR′)—NR—CO—; R and R′ independentlyrepresent an optionally substituted aliphatic, cycloaliphatic, aromatic,heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkylgroup having from 1 to about 20 carbon atoms; and R and R′ may becombined to form, together with the N atoms to which they are attached,an optionally substituted and/or fused 5- to 7-membered ring; the groupsX may be the same or different and represent halogen, isocyanate andCOOH; the groups Y may be the same or different and are selected fromOH, NO₂, CN, groups of formula R″, OR″, COOR″, OCOR″, CONHR″, CON(R″)₂,OCONHR″, OCON(R″)₂, COR″, SO₃H, SO₃R″, SO₂NHR″, SO₂N(R″)₂, NHCOR″,NRCOR″, NHCOOR″, NRCOOR″, NHSO₂R″, NRSO₂R″, NHR″, and N(R″)₂, whereinthe groups R″ may be the same or different and represent an optionallysubstituted aliphatic, cycloaliphatic, aromatic, heteroaromatic,alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkyl group havingfrom 1 to about 20 carbon atoms and may also be combined to form,together with the N atom to which they are attached, an optionallysubstituted and/or fused 5- to 7-membered ring; n and p each represent 0or an integer of from 1 to 8, provided that (n+p) is not higher than 8and further provided that for n=0 at least one of R, R′ and R″ comprisesat least one group X as substituent; provided that at least one group Xrepresents a group of formula -L-P wherein L represents a covalent bondor a bridging group and P represents a polymer molecule.
 6. Thepolymer-bonded quaterrylene or terrylene dye of claim 5, wherein the orat least one of the groups Z represents N—R.
 7. The polymer-bondedquaterrylene or terrylene dye of claim 6, wherein R is selected fromoptionally substituted alkyl having from 1 to about 6 carbon atoms,optionally substituted alkylaryl or arylalkyl having from 7 to about 12carbon atoms, optionally substituted aryl having from about 6 to about20 carbon atoms, and optionally substituted heteroaryl having from about3 to about 20 carbon atoms.
 8. The polymer-bonded quaterrylene orterrylene dye of claim 6, wherein R is selected from optionallysubstituted alkyl having from 1 to about 4 carbon atoms, optionallysubstituted phenyl, or optionally substituted benzyl.
 9. Thepolymer-bonded quaterrylene or terrylene dye of claim 6, wherein Rrepresents phenyl substituted with from 1 to about 3 groups selectedfrom halogen and alkyl having from 1 to about 6 carbon atoms.
 10. Thepolymer-bonded quaterrylene or terrylene dye of claim 9, wherein thephenyl is substituted at least with two alkyl groups which comprise asecondary or tertiary carbon atom.
 11. The polymer-bonded quaterryleneor terrylene dye of claim 10, wherein the alkyl groups which comprise asecondary or tertiary carbon atom are selected from isopropyl andtert.-butyl groups.
 12. The polymer-bonded quaterrylene or terrylene dyeof claim 5, wherein the quaterrylene or terrylene dye is a compound offormula (C).
 13. The polymer-bonded quaterrylene or terrylene dye ofclaim 5, wherein the quaterrylene or terrylene dye is a compound offormula (A) and formula (B) wherein the groups Z may be the same ordifferent and represent O or N—R.
 14. The polymer-bonded quaterrylene orterrylene dye of claim 5, wherein L is selected from O, COO, OCO, CONH,and NHCOO.
 15. The polymer-bonded quaterrylene or terrylene dye of claim14, wherein L represents O.
 16. The polymer-bonded quaterrylene orterrylene dye of claim 5, wherein P represents a polymer molecule thatcomprises at least one monomer unit comprising at least one polar group.17. The polymer-bonded quaterrylene or terrylene dye of claim 16,wherein the at least one polar group is selected from hydroxy, carboxyand amino groups.
 18. The polymer-bonded quaterrylene or terrylene dyeof claim 5, wherein the polymer comprises a phenolic resin of formula

wherein the groups R₄ may be the same or different and are selected fromalkyl groups having from 1 to about 10 carbon atoms and the averagenumber of m is from about 1 to about
 30. 19. The polymer-bondedquaterrylene or terrylene dye of claim 18, wherein R₄ is selected fromtert-butyl, tert-octyl and branched nonyl.
 20. The polymer-bondedquaterrylene or terrylene dye of claim 5, wherein P has more than oneperylene dye molecule bonded thereto.
 21. The polymer-bondedquaterrylene or terrylene dye of claim 5, wherein P has from 1 to about6 quaterrylene and/or terrylene dye molecules bonded thereto.
 22. Aprocess for making a polymer-bonded quaterrylene or terrylene dyeaccording to claim 5, wherein the process comprises contacting aquaterrylene or terrylene dye of formula (A), (B) or (C):

wherein the groups Z, the same or different from each other, representO, S or N—R, provided that in the above formulae the unit —CO—Z—CO—(inthe case of formula (A) or formula (B) one or both units of formula—CO—Z—CO—) may be replaced by a unit —CS—Z—CO—, or a unit —CS—Z—CS—, orby [—COOH HOOC—] (i.e., the dicarboxylic acid instead of the cyclicanhydride) and further provided that for Z═N—R a unit —CO—Z—CO-may bereplaced by a unit of formula —C(═NR′)—NR—CO—; R and R′ independentlyrepresent an optionally substituted aliphatic, cycloaliphatic, aromatic,heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkylgroup having from 1 to about 20 carbon atoms; and R and R′ may becombined to form, together with the N atoms to which they are attached,an optionally substituted and/or fused 5- to 7-membered ring; the groupsX may be the same or different and represent halogen, isocyanate andCOOH; the groups Y may be the same or different and are selected fromOH, NO₂, CN, groups of formula R″, OR″, COOR″, OCOR″, CONHR″, CON(R″)₂,OCONHR″, OCON(R″)₂, COR″, SO₃H, SO₃R″, SO₂NHR″, SO₂N(R″)₂, NHCOR″,NRCOR″, NHCOOR″, NRCOOR″, NHSO₂R″, NRSO₂R″, NHR″, and N(R″)₂, whereinthe groups R″ may be the same or different and represent an optionallysubstituted aliphatic, cycloaliphatic, aromatic, heteroaromatic,alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkyl group havingfrom 1 to about 20 carbon atoms and may also be combined to form,together with the N atom to which they are attached, an optionallysubstituted and/or fused 5- to 7-membered ring; n and p each represent 0or an integer of from 1 to 8, provided that (n+p) is not higher than 8and further provided that for n=0 at least one of R, R′ and R″ comprisesat least one group X as substituent; with a polymer P under conditionswhich cause a reaction of a group X of the quaterrylene or terrylene dyewith a functional group of the polymer to covalently bind the polymer tothe quaterrylene or terrylene dye.
 23. A polymer-bonded quaterrylene orterrylene dye of one of formulae (I) to (IX):

wherein the groups Z, the same or different from each other, representO, S or N—R, provided that in the above formulae the unit —CO—Z—CO— (inthe case of formula (I) or (II) one or both units of formula —CO—Z—CO—)may be replaced by a unit —CS—Z—CO—, or a unit —CS—Z—CS—, or by [—COOHHOOC—] (i.e., the dicarboxylic acid instead of the cyclic anhydride) andfurther provided that for Z═N—R a unit —CO—Z—CO-may be replaced by aunit of formula —C(═NR′)—NR—CO—; R and R′ independently represent anoptionally substituted aliphatic, cycloaliphatic, aromatic,heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkylgroup having from 1 to about 20 carbon atoms; and R and R′ may becombined to form, together with the N atoms to which they are attached,an optionally substituted and/or fused 5- to 7-membered ring; R₁, R₂ andR₃ are independently selected from hydrogen, optionally substitutedC₁-C₄ alkyl, optionally substituted C₁-C₄ alkyl-COOH, optionallysubstituted C₁-C₄ alkyl-SO₃H, optionally substituted C₁-C₄ alkoxy,optionally substituted mono(C₁-C₄)alkylamino, optionally substituteddi(C₁-C₄)alkylamino, optionally substituted C₁-C₄ aminoalkyl, halogen,cyano, nitro, and SO₃H; the groups X may be the same or different andrepresent halogen, isocyanate and COOH; the groups Y may be the same ordifferent and are selected from OH, NO₂, CN, groups of formula R″, OR″,COOR″, OCOR″, CONHR″, CO(NR″)₂, OCONHR″, OCO(NR″)₂, COR″, SO₃H, SO₃R″,SO₂NHR″, SO₂N(R″)₂, NHCOR″, NRCOR″, NHCOOR″, NRCOOR″, NHSO₂R″, NRSO₂R″,NHR″, and N(R″)₂, wherein the groups R″ may be the same or different andrepresent an optionally substituted aliphatic, cycloaliphatic, aromatic,heteroaromatic, alkylaryl, alkylheteroaryl, arylalkyl or heteroarylalkylgroup having from 1 to about 20 carbon atoms and, where two groups R″are present, may also be combined to form, together with the N atom towhich they are attached, an optionally substituted and/or fused 5- to7-membered ring; in the case of formulae (V), (VII) and (IX) n and peach represent 0 or an integer of from 1 to 8 (i.e., 1, 2, 3, 4, 5, 6, 7or 8), provided that (n+p) is not higher than 8; and in the case of theremaining formulae n and p each represent 0 or an integer of from 1 to 7(i.e., 1, 2, 3, 4, 5, 6 or 7), provided that (n+p) is not higher than 7;and P represents a polymer molecule.
 24. The polymer-bonded quaterryleneor terrylene dye of claim 23, wherein P comprises a phenolic resin orphenol formaldehyde resin of formula

wherein the groups R₄ may be the same or different and are selected fromalkyl groups having from 1 to about 10 carbon atoms and the averagenumber of m is from about 4 to about
 30. 25. A process for making apolymer-bonded quaterrylene and/or terrylene dye of claim 23, whereinthe process comprises contacting at least one compound of one offormulae (I′) to (IX′):

wherein R₁, R₂, R₃, X and Y are as defined in claim 23 and (n+p) is nothigher than 8 with a polymer of formula P wherein P is a polymermolecule which comprises a group which is capable of reacting with X toreplace X by a group of formula OP.
 26. A printing ink composition,wherein the composition comprises a polar liquid medium and at least onepolymer-bonded quaterrylene and/or terrylene dye of claim 4 dissolved ordispersed in the medium.
 27. A marking or security feature which is madewith the printing ink composition of claim
 26. 28. A marking or securityfeature which comprises at least one polymer-bonded perylene dye ofclaim
 4. 29. An article which comprises the marking or security featureof claim
 27. 30. The article of claim 29, wherein the article is atleast one of a can, a metal, an aluminum foil, a cartridge, a capsule,an article made of glass, an article made of ceramic, a packaging, abanknote, a passport, a security document, a value document, a ticket, athread, a label, a card, and a commercial good.
 31. A method ofauthenticating an article, wherein the method comprises providing thearticle with the marking or security feature of claim
 27. 32. A methodof authenticating an article, wherein the method comprises applying ontothe article the printing ink composition of claim
 26. 33. A dye-dopedpolymer, wherein at least about 0.1% of the polymer molecules havebonded thereto at least one quaterrylene and/or at least one terrylenedye and wherein the polymer is produced by the process of claim
 22. 34.The polymer of claim 33, wherein the polymer comprises a phenolic resinof formula

wherein the groups R₄ may be the same or different and are selected fromalkyl groups having from 1 to about 10 carbon atoms and the averagenumber of m is from about 1 to about
 30. 35. A liquid medium compositioncomprising a liquid medium and at least one polymer-bonded quaterryleneand/or terrylene dye of claim 4 dissolved or dispersed in the medium.